Controlled nitroxide-mediated radical polymerization of methyl and phenyl vinyl ketone

Abstract

The article describes unprecedented nitroxide-mediated radical polymerization of methyl and phenyl vinyl ketone (MVK and PVK) using a sterically highly hindered alkoxyamine as initiator/regulator. It is shown that controlled polymerization of PVK is far more difficult to achieve than controlled MVK polymerization. Whereas for MVK high conversion resulting in polyvinyl ketone with low polydispersity index is readily obtained, the PVK polymerization provides good results only in the presence of free nitroxide and styrene as additives. Vinyl ketone polymerizations are analyzed by ESI mass spectrometry. These MS studies provide insights into the problems associated with the controlled nitroxide-mediated polymerization of PVK. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 This article describes nitroxide-mediated polymerization (NMP) of methyl vinyl ketone (MVK) and phenyl vinylketone (PVK) using alkoxyamine 1 as initiator/regulator. NMP of MVK occurs well controlled. However, for controlled NMP of PVK, styrene and free nitroxide are necessary as additives. Mass spectrometric analysis is used to investigate the polymerization process. Copyright © 2012 Wiley Periodicals, Inc.